DE4116609C2 - - Google Patents

Description

The invention relates to a method for the production of ceramic Trays as a mold, wherein

• a) a fusible or triggerable model of a casting part is produced,
• b) the model in a slurry from a slurry a refractory material and a binder containing a Dispersion of aqueous, colloidal silica sol and polymers contains, is immersed to a damp Coating on the model to form
• c) a coarse refractory powder is applied to the coating is speckled,
• d) the coating is dried,
• e) the steps b), c) and d) are repeated until the Shell has reached the desired thickness.

The invention also relates to a binder according to the preamble of claims 10 and 11.

In such a process, model grapes are made Wax or the like by applying several dipping Coatings with a stable ceramic layer of some Millimeters thick. The individual layers become each dried or cured. On the individual moist dip layers becomes coarse, refractory powder or Sand as a link to the following dip layer  sprinkled. The peels are fired after dewaxing and can then be poured off warm or after cooling become.

Process of the type described above, with the aq work is limited by the fact that aqueous binders as opposed to alcoholic binders require very long drying and ultimately even to complete drying of a corresponding vacuum drying had to be subjected. One tried, by interfering of alcohol, eg. As isopropanol, in the aqueous binder this To avoid difficulties. The alcohol replaced a part of water and had the property faster than water to evaporate. However, alcohol did not Prevents the already dipped and dried Layer on subsequent dipping the water-alcohol Ge mixed in again and thus as the dew progresses ever longer drying times were required. you has also tried in other ways, the upcoming problems to solve.

From US Pat. No. 3,058,244 it is known to add resinous polymers to a 30% aqueous silica sol binder in the amount such that the solids content of the binder thus formed consists of 60-80% by weight of SiO ₂ and 8- 35 wt .-% resinous polymer. Ceramic bowls, which are made with this binder, have inter alia by the poly merzusatz an increased green strength of the shell, where by the interposition of an autoclave, the melting of the wax from the shell should be possible.

US Patent 31 26 597 describes a ceramic shell with an aqueous binder based on silica (30 wt .-%), the to dilute water and to accelerate the sol / gel Reaction sodium fluoride is added. The sodium fluoride only requires a faster curing of the individual applied ceramic layers, but does not prevent  the penetration of the aqueous binder in the subsequent Dive into the previous ceramic layers. These Binder combination requires long drying times and at Cups with higher number of layers ultimately vacuum drying.

US Pat. No. 3,165,799 describes a triple immersion process for producing a ceramic shell for core-rich investment casting, in which the first ceramic immersion layer is applied with an aqueous binder followed by sanding. Thereafter, a second ceramic immersion layer with aqueous binder, the 0.5-2 wt .-% polyvinyl alcohol are added, applied without sanding. Thereafter, the application of a third ceramic immersion layer, consisting of the aqueous SiO ₂ binder with 0.5-2 wt .-% polyvinyl alcohol with final Beschandung. The above dipping sequence has the advantage that you can manufacture precision castings with core parts that are otherwise adjustable only by ceramic cores forth.

From US Pat. No. 3,752,689, the production of a ceramic shell in a rapid process using an aqueous binder containing 26.4% by weight of SiO ₂ and 4.2% by weight of Al ₂ O _{3 is} known, organic binders being used or inorganic bases is converted from the sol to the gel state. This method allows relatively quick application of the individual ceramic layers, but has the disadvantage that each ceramic layer is infiltrated by the subsequent applied ceramic layer through the aqueous binder and that a lengthy final drying, inter alia, must be carried out in vacuo. The idea is to discharge the acidic SiO ₂ / Al ₂ O ₃ sol which is positively charged by negatively charged particles of organic and inorganic bases.

US Patent 38 59 153 also describes a Schnellverfah ren for producing a ceramic shell, in which a aqueous binder with negatively charged colloidal particles by an aqueous sol with positively charged colloidal Particles discharged and thus cured. This too  Method allows the rapid application of the individual Ke ramikschichten, however, has the disadvantage that a Discharge of the negatively charged sol by the applied positively charged sol can already take place in the immersion tank. Also, this method has the disadvantage that the thus produced shell of a correspondingly long end drying must be subjected. Another disadvantage is that the shells by continuous infiltration with diving watery binder so heavy that it is at risk of breakage are. Subsequent vacuum drying is off For economic reasons unavoidable.

US Pat. No. 3,894,572 describes the production process for a ceramic shell with a positively charged aqueous Binder, by the sanding material, which is negative contains charged colloidal particles, is cured. The Disadvantages are the same as those we mentioned above have described both fast method.

US-Patent 39 33 190 describes a process for the preparation of a pure Al ₂ O ₃ -shell for the directional solidification. The ceramic dish is dressed with 15-25 parts of an aqueous solution containing 15% by weight of aluminum polyoxychloride, 6-10 parts of water and 8-14 parts of latex. To this liquid is added as a filler Al ₂ O ₃ flour. For pH control of the binder, 0.5-1.5 parts of a 2% aqueous HCl solution are added. In this case, the addition of latex has the function of increasing the green strength of the applied ceramic layers. All the disadvantages described for the rapid process are also relevant to this shell.

From DE 25 19 309 A1 discloses a process for the preparation of forms by repeating a shape model with a liquid A and a liquid B alternately or simultaneously coated, the liquid A including an organic paste resin containing  Metal oxide sol, in particular a silica sol or a by adding a refractory material to said sol produced slurry and the liquid B is a gelling agent represents the components of the liquid A. at an application of the dipping method for coating the Form results in that there is a gelation of the two Liquids come.

EP 03 99 727 A1 describes a ceramic molding material Hollow grains or bubbles of refractory material with a hardened ceramic slurry is bound.

The object of the invention is a generic method and specify a binder with the fast-drying Shells can be made, with the drying time is comparable to the drying time of peels on based on alcoholic binders.

This object is achieved in that the binder synthetic high polymers and / or an emulsifier from the group of organosilicon compounds is added so that a coating is formed, which after the Dry impermeable, but water vapor permeable is.

When using high polymers, in particular high polymers with hydrophobic and / or hydrophobic character, ent stands on the dip layer, which also serves as a back-up layer is called, a film that is impermeable to water is permeable to water vapor, however, and thus one final drying or subsequent drying of the ceramic Layers that form the shell are allowed. Will be a new one Dipping layer applied, so the binder of the following Applied wet dip not in the already dried or partially dried and sanded dipping penetrate layer. Drying the still humid dipping Layers can in the usual way, if necessary with Venti lator assistance. The green strength of the sun produced ceramic bowls is also satisfactory like the firmness after firing. skin defects due to cracks or hot cracks in the castings will not observed.  

By appropriate dosage of the synthetic high polymers and / or an emulsion from the group of organosilicon compounds with respect to the aqueous silica sol and also by variation of the refractory material, which as Filler is used, the dip mass can be the respective Ver conditions or requirements. In this connection In the meantime, a proposal of the invention is that the Binder 2-20% by volume, in particular 14-18% by volume, of synthe contains tables high polymers. Another proposal looks before that the binder 2-20 vol .-%, in particular 3-7 vol .-% a synthetic high polymer containing an addition of 0.2-20 wt .-%, based on the weight of the synthetic Hochpolymers, an emulsion from the group of siliciumor ganic compounds is mixed.

It has proven to be beneficial to use an emulsion from the Group of organosilicon compounds with droplets sizes of <200 nm. In addition, the aqueous colloidal silica sol 0-20% by weight of the total water content of Binders, in particular 0.005-15 wt .-% of an emulsion the group of organosilicon compounds.

Furthermore, the binder can also relaxer, esp in particular in an amount of 0.08 vol.%, based on the Submersible mass amount to be added. The relaxant promotes the uniform distribution of colloidal pebbles sol, high polymer and / or an emulsion from the group of organosilicon compounds and improves the wetting availability of the dip without the silica sol, the Hochpo lymere and / or the emulsion from the group of silicon be attacked organic compounds.

To segregate the colloidal silica sol and high It may be advantageous to avoid polymers during long storage be liable, the dispersion of aqueous silica sol and synthetic high polymers only shortly before use to manufacture and to process the dipping mass.  

A high polymer, which has the desired properties has the following characteristics:

solid 50 ± 1% by weight Viscosity at 20 ° C (D = 57 ^-1 ) 800-1500 mPa · s PH value 7.0-8.5 density about 1.02 g / cm³ film properties viscoplastic, waterproof, alkali-resistant

An emulsion of organosilicon compounds, the ge has desired properties, has the following Kennda th:

Solids 52-57% by weight viscosity 25 mPa · s density about 1 g / cm³ solvent water PH value 7-9

In the following the invention with reference to embodiments explained.

Characteristics of the method according to the invention Binder: about 30% colloidal silica sol or other aqueous colloidal silica sols   Thinner: If necessary, deionized water High polymer as a film-forming agent: z. B. aqueous high polymer dispersion having a hydrophobic and / or hydrophobic character and / or an emulsion from the group of organosilicon compounds Ink pen: Filler is the ceramic refractory additive added to the high polymer colloidal silica binder and / or an organosilicon compound emulsion to produce the back-up dip. It consists of about 45 wt .-% of fused silica - 120 mesh to <350 mesh, about 45 wt .-% mullite 150 mesh and about 10 wt .-% zirconium silicate 350 mesh Sanding material for the 1st and 2nd layer: Zirconium silicate sand Sanding material for the 3rd layer: Aluminum silicate   3rd layer = 1st back-up layer @ Sanding material for the 4th - nth layer: Mixture of 50% mullite and 50% aluminum silicate, grain size 0.3-1.0 mm

1st example

In a mixing tank of 600 mm diameter and 630 mm Altitude was set the following back-up diving mass:

1. binder 41.5% by weight = 94 kg 2nd filler 58.5% by weight = 132 kg 3. Total @ Back-up immersion mass 141 l = 226 kg

4. The 94 kg binder, corresponding to 82 l, consist of:

56 liters of aqueous colloidal 30% silica sol
13 liters of deionized water
13 l of high polymer

5. The 132 kg fillers consist of:

59.5 kg fused silica flour <350 mesh 59.5 kg mullite flour 150 mesh 13 kg of zircon flour 350 mesh

The result was a cup outlet viscosity according to Zahncup 2 of 22 sec. By increasing the proportion of filler to 63 wt .-% the outlet viscosity after Zahncup 2 was at 37 s increased and was therefore within the target phasing out viscosity of 33-41 s.  

There were wax grapes from the production and 2 grapes Bend samples as usual with the 1st and 2nd dipping coat and then with the back-up dipping mass above Zusam dipped as follows:

• 1. Diving for the 1st back-up layer in the Back-up dipping mass and Besanden with Al-silicate, grain size 0.3-0.5 mm, by hand
• 2. Drying of the applied back-up dip 2.5 to 3 hours
• 3. Diving for the 2nd back-up layer in the Back-up dipping mass and sanding with 50% Al silicate and 50% mullite 0.3-1 mm grain size by hand
• 4. Drying as under 2.
• 5. 3rd, 4th and 5th back-up layer as under 3. and 4. This means that the cups in the 2-shift operation was completed.

The relative humidity was 50 ± 5%, ambient temperature = 23 ° ± 1 ° C. The drying took place partially with fan support.

The applied core-rich castings were of very good Quality. The following mean bending fractions were confirmed measured on ceramic flat samples:

Condition of the ceramic flat samples σ _BB green 349 N / cm²   burned 309 N / cm² Burned and dived 400 N / cm²

2nd example

It was in a production mixing container following baking mixed up dipping mass:

1. binder 37% by weight = 423 kg 2nd filler 63% by weight = 720 kg 3. Total amount of back-up dip 630 l = 1143 kg

4. The 423 kg binder, corresponding to 367 l, consist of:

251 l of aqueous colloidal 30% silica sol
58 l of deionized water
58 l high polymer

5. The 720 kg fillers consist of:

327.5 kg fused silica flour <350 mesh 327.5 kg of mullite flour 150 mesh 65 kg fused silica 350 mesh

The pH of the finished back-up dip was between 9-10 units. The actual viscosity was within the target viscosity, namely between 33 and 41 s according to Zahncup 2. The calculated solids content of colloidal SiO ₂ in the binder was set to 21.5%. The calculated solids content of the high polymer content in the binder was about 7%. The total solids amount of colloidal SiO ₂ and high polymer in the binder was about 28.5%.

Relative air humidity of the diving room 50 ± 5%.

Dive room temperature 23 ° ± 1 ° C.

Drying time between the back-up layers = 2.5 to 3 Hours.

The following dive rhythm was after the 1st and 2nd Tauchüber Train maintained by robot:

• 1. Diving for the 1st back-up layer in the back-up Dipping mass and sanding with Al silicate, grain size 0.3 up to 0.5 mm, by robot.
• 2. Drying of the applied back-up layer 2.5 to 3 Hours.
• 3. Diving for the 2nd back-up layer in the back-up Dipping mass and sanding with 50% Al silicate and 50% Mullite 0.3-1 mm grit by robot.
• 4. Drying as under 2.
• 5. 3rd, 4th and 5th back-up layer as under 3rd and 4th

The corresponding trays were in 2-shift operation fer tiggestellt. A total of 1334 grapes were produced.

The following average fracture bending strength values (σ _BB ) were measured on ceramic flat samples:

Condition of the ceramic flat samples σ _BB green 450-660 N / cm² burned 480-710 N / cm²   Burned and dived 590-870 N / cm²

3rd example

In a production mixing vessel, the following back-up Dipping mass mixed:

1. binder 36% by weight = 434.8 kg 2nd filler 64% by weight = 737.7 kg 3. Total amount of back-up dip 636.7 l = 1172.5 kg

4. The 360.2 l binders consist of:

247 l of aqueous colloidal 30% silica sol
57.2 liters of deionized water
56 l high polymer

5. The 737.7 kg filler consists of:

335.3 kg fused silica flour <120 mesh 335.3 kg of mullite flour 150 mesh 67.1 kg of zirconium silicate 350 mesh

The pH of the finished back-up dip was between 9-10 units. The actual viscosity was in the context of interim time for manufacturing reasons modified target viscosity, namely between 28 and 36 s after tooth cup second The total solids of colloidal SiO ₂ and high polymer in the binder was 28.25%.

Relative air humidity of the diving room 50 ± 5%.

Dive room temperature 23 ° ± 1 ° C.  

Drying time between the back-up layers = 2.5 to 3 hours

The following dive rhythm was after the 1st and 2nd Tauchüber Train maintained by robot:

• 1. Diving for the 1st back-up layer in the back-up Dipping mass and sanding with Al silicate, grain size 0.3 up to 0.5 mm, by robot.
• 2. Drying of the applied back-up layer 2.5 to 3 Hours.
• 3. Diving for the 2nd back-up layer in the back-up Dipping mass and sanding with 50% Al silicate and 50% Mullite 0.3-1.0 mm grit by robot.
• 4. Dry as in 2.
• 5. 3rd, 4th and 5th back-up layer as under 3rd and 4th

The corresponding trays were in 2-shift operation fer tiggestellt. A total of 333 grapes were produced.

The following average fracture bending strength values (σ _BB ) were measured on ceramic flat samples:

Condition of the ceramic flat samples σ _BB green 417 N / cm² burned 582 N / cm² Burned and dived 696 N / cm²

4th example

In a mixing tank of 600 mm diameter and 630 mm Altitude was set the following back-up diving mass:

1. binder 36% by weight = 73.7 kg 2nd filler 64% by weight = 130.9 kg 3. Total amount of back-up dip 113 l = 204.6 kg

4. The 73.7 kg, corresponding to 61.6 l, consisting of:

58.7 l of aqueous colloidal 30% silica sol
2.9 l high polymer with additive

5. The 130.9 kg filler consisting of:

59.5 kg fused silica flour -120 mesh 59.5 kg mullite flour 150 mesh 11.9 kg zirconium silicate 350 mesh

The result was a cup outlet viscosity according to Zahncup 2 from 43 s. By lowering the filler content to approx. 61 Wt .-%, the outlet viscosity was lowered to 36 s and was within the target phasing out viscosity of 28-36 sec.

There were wax grapes from the production and 2 grapes Bend samples as usual with the 1st and 2nd dipping coat and then with the back-up dipping mass above Zusam dipped as follows:

• 1. Diving for the 1st back-up layer in the back-up Dipping mass and sanding with Al silicate, grain size 0.3 up to 0.5 mm, by hand.  
• 2. Drying the applied back-up dipping mass 2.5 to 3 hours.
• 3. Diving for the 2nd back-up layer in the back-up Dipping mass and sanding with 50% Al silicate and 50% Mullite, 0.3-1 mm grain, by hand.
• 4. Drying as under 2.
• 5. 3rd, 4th and 5th back-up layer like 3rd and 4th This means that the shells are in 2-shift operation were completed.

The relative humidity was 50 ± 5%, ambient Temperature = 23 ° ± 1 ° C.

The drying took place partially with fan support Zung.

The applied core-rich castings were of very good Quality.

The following mean flexural strength values were determined measured ceramic flat samples:

Condition of the ceramic flat samples σ _BB green 366-394 N / cm² burned 558-684 N / cm² Burned and dived 725-807 N / cm²

5th example

In a production mixing vessel, the following back-up Dipping mass applied:  

1. binder 37% by weight = 426 kg 2nd filler 63% by weight = 726 kg 3. Total amount of back-up dip 637 l = 1152 kg

4. The 426 kg binder, corresponding to 360 l, consist of:

331 l of aqueous colloidal 30% silica sol
29 l emulsion of an organosilicon compound

5. The 726 kg fillers consist of:

330 kg fused silica flour <120 mesh 330 kg of mullite flour 150 mesh 66 kg zircon flour 350 mesh

The pH of the finished back-up dip was between 9 and 10 units. The actual viscosity was within the Target viscosity, namely between 24 and 28 s after Tooth Cup 2.

The relative humidity of the diving room was 50 ± 5%.

The temperature of the diving room was 23 ° ± 1 ° C.

The drying time between the back-up layers was 2.5 up to 3 hours.

The following dive rhythm was after the 1st and 2nd Tauchüber Train maintained by means of robots.

• 1. Diving for the 1st back-up layer in the back-up Dipping mass and sanding with Al silicate, grain size 0.3 up to 0.5 mm, by robot.
• 2. Dry the applied back-up layer over 2.5 up to 3 hours.  
• 3. Diving for the 2nd back-up layer in the back-up Dipping mass and sanding with 50% Al silicate and 50% Mullite, grain size 0.3 to 1.0 mm, using Robot.
• 4. Drying as under 2.
• 5. 3., 4. and 5. Back-up-layer as in 3. and 4.. The corresponding trays were in 2-shift operation prepared.

The following fracture bending strength values (σ _BB ) were measured on Ke ram flat samples:

Condition of the ceramic flat samples σ _BB green 400-600 N / cm² burned 470-690 N / cm² Burned and dived 620-750 N / cm²

Claims (13)

1. A method for producing ceramic shells as a casting mold, wherein

• a) a fusible or triggerable model of a part to be cast is produced,
• b) dipping the model into a slurry of a refractory material and a binder containing a dispersion of aqueous colloidal silica sol and polymers to form a wet coating on the model;
• c) a coarse, refractory powder is sprayed onto the coating,
• d) the coating is dried,
• e) repeating steps b), c) and d until the shell has reached the desired thickness,

characterized in that the binder synthetic high polymers and / or an emulsion from the group of the organosilicon compounds is or are added, so that a coating is formed which is impermeable to water after drying, but permeable to water vapor. 2. The method according to claim 1, characterized by the Use of a high polymer and / or an emulsion from the group of organosilicon compounds with hydrophobic and / or hydrophobic character.   3. The method according to claim 1 or 2, characterized net that the binder 2 to 20 vol .-%, in particular 14- 18 vol .-%, containing synthetic high polymers. 4. The method according to claim 1, characterized by the Use of an emulsion from the group of silicon organic compounds with droplet sizes of these Compounds of <200 nm. 5. The method according to claim 1 or 4, characterized net, that the aqueous colloidal silica sol 0-20 wt .-% from the total water content of the binder, in particular 0.005-15 wt .-% of an emulsion from the group of sili contains organometallic compounds. 6. The method according to any one of claims 1 to 5, characterized characterized in that the binder 2-20 vol .-%, in particular Contains 3-7 vol.% Of a synthetic high polymer, an addition of 0.2-20 wt .-%, based on the weight of the synthetic high polymer, an emulsion from the group of organosilicon compounds admixed is. 7. The method according to at least one of the preceding An claims, characterized in that the binder a Relaxing agent is added. 8. The method according to claim 7, characterized in that the relaxant in an amount of 0.08 vol.%, based on the Tauchmassenmenge added. 9. The method according to at least one of the preceding An claims, characterized in that the dispersion of aqueous silica sol and synthetic high polymers made just before their use and for diving mass is processed.   10. A binder for a dip material for the production of ceramic shells as a casting mold using the method steps a) to e) of the preamble of claim 1, characterized in that the binder is a synthetic high polymer having the following characteristics: solid 50 ± 1% by weight Viscosity at 20 ° C (D = 57 ^-1 ) 800-1500 mPa · s PH value 7.0-8.5 density about 1.02 g / cm³ film properties viscoplastic, waterproof, alkali-resistant is added, so that on the model a coating is formed, which is impermeable to water after drying, but permeable to water vapor. 11. binder for a dip material for the production of ceramic shells as a casting mold using the process steps a) to e) of the preamble of claim 1, characterized in that the binder is an emulsion from the group of organosilicon compounds having the following characteristics: Solids 52-57% by weight viscosity 25 mPa · s density about 1 g / cm³ solvent water PH value 7-9 is added, so that on the model a coating is formed, which is impermeable to water after drying, but permeable to water vapor. 12. Binder according to claim 10 or 11, comprising at least one of the in claims 2 to 8 specified compositions.